Contamination by polybrominated diphenyl ethers of sediments from the Lake Maggiore basin (Italy and Switzerland)

Polybrominated diphenyl ethers (PBDEs) are characterized by chemical properties and toxicological profiles similar to other POPs (persistent organic pollutants) included in the EU Priority Pollutant List (2455/01/CE). However, limited data have been available for these compounds thus far for Italian freshwater abiotic matrices. Lake Maggiore basin, a heavily industrialized and densely populated area, was selected for studying PBDE contamination in Italy. PBDEs and OCs (organochlorine compounds) in the basin were quantified by analysing both sediment cores collected in 2005 from the lake and grab samples from the main tributaries and the emissary. Fourteen PBDEs, from tri-BDE to hepta-BDE congeners and BDE209, were compared with some organochlorine POPs (PCBs and DDTs) characterizing Lake Maggiore basin contamination. Analyses of tri-to hepta-BDEs, PCBs and DDTs were undertaken by GC-MS/MS, while BDE-209 was analysed by GC/ECD. Results showed a dominant presence of BDE-209 (>95% of SigmaBDE) and limited amounts of BDE-47, BDE-99, BDE-100, BDE-153 and BDE-154. Lake core profiles highlighted a decreasing trend in PCB concentrations starting from the year 2000, while PBDEs showed greater concentrations after the beginning of the 1990s (up to 30 ng g(-1)d.w.). Among the tributaries, the Bardello and Boesio rivers were the most PBDE-contaminated (up to 290 ng g(-1)d.w.).     

On the effect of pH in aromatic photonitration upon nitrate photolysis

This paper studies the pH effect on the photonitration of catechol, 1-naphthol, naphthalene, and benzene. The pH trend is influenced by the generation of HNO(2) and peroxynitrous acid (HOONO) upon nitrate photolysis. HNO(2) can be involved in a direct and an indirect nitration process. Direct nitration follows the pH distribution of HNO(2) (flexus around 3). Indirect nitration, possibly involving nitrosation+oxidation, would be highest around pH3. HOONO can be involved in electrophilic nitration, where the initial formation rate of the nitroderivatives is proportional to [H(+)], or take part in nitration directly, in which case a less important pH effect in photonitration is observed. The relative importance of the various nitration pathways for each substrate determines the resulting pH effect in photonitration upon nitrate photolysis.     

Analysis of volatile organic compounds (VOCs) in sediments using in situ SPME sampling

A new method of determining the composition of sediment/soil gases and their volatile organic compound (VOC) content is described. VOCs were collected in situ from intertidal sediments in the Menai Strait and surrounding areas. The sampling was performed using a portable sampler comprising a funnel coupled to a SPME fibre. Gases were extracted from the sediments using a small vacuum pump pulling 100 mL min(-1) at atmospheric pressure. Sixty one different compounds were detected in the samples, and their fluxes and concentrations were determined. The compounds were classified into groups: halogenated, sulfur containing compounds, aldehydes, BTEXs (benzene, toluene, ethyl benzene and xylene) and aliphatic hydrocarbons. Results of principal component analysis (PCA) showed that the chemical composition of extracted gas was influenced primarily by sediment type. Muddy anoxic sediments were dominated by halogenated and sulfur containing compounds and sandy sediments had more aldehydes and BTEXs.     

Air pollutants and the characterization of the organic content of aerosol particles in a mixed industrial/semi-rural area in central Italy

Both regulated and unregulated air pollutants were detected during an intensive seasonal sampling campaign in a mixed industrial/semi-rural area on the outskirts of Rome, Italy, at two sites located opposite a hospital waste incinerator, downwind according to the direction of the prevailing local winds. Concentrations of pollutants were significantly lower than in urban atmospheres. The composition of particulate organic material indicated a heavy biogenic impact, accompanied by a lower contribution from petroleum-related processes. Both PAH and nitro-PAH group compositions of particulates were used to assess the nature and relative importance of sources. Both sites showed that different and diffuse sources contributed to local pollution with a significant contribution from traffic, proving that the hospital waste incinerator was not the main pollution source in this area. Among unregulated compounds, a series of positional isomers of nitro-PAHs and other organic compounds associated with particulate matter were investigated. In particular, 1- and 3-nitrophenanthrene identification was carried out, and they proved to be the most abundant nitro-PAHs.     

Soil organic carbon sequestration as affected by afforestation: the Darab Kola forest (north of Iran) case study

Following the ratification of the Kyoto Protocol, afforestation of formerly arable lands and/or degraded areas has been acknowledged as a land-use change contributing to the mitigation of increasing atmospheric CO(2) concentration in the atmosphere. In the present work, we study the soil organic carbon sequestration (SOCS) in 21 year old stands of maple (Acer velutinum Bioss.), oak (Quercus castaneifolia C.A. Mey.), and red pine (Pinus brutia Ten.) in the Darab Kola region, north of Iran. Soil samples were collected at four different depths (0-10, 10-20, 20-30, and 30-40 cm), and characterized with respect to bulk density, water content, electrical conductivity, pH, texture, lime content, total organic C, total N, and earthworm density and biomass. Data showed that afforested stands significantly affected soil characteristics, also raising SOCS phenomena, with values of 163.3, 120.6, and 102.1 Mg C ha(-1) for red pine, oak and maple stands, respectively, vs. 83.0 Mg C ha(-1) for the control region. Even if the dynamics of organic matter (OM) in soil is very complex and affected by several pedo-climatic factors, a stepwise regression method indicates that SOCS values in the studied area could be predicted using the following parameters, i.e., sand, clay, lime, and total N contents, and C/N ratio. In particular, although the chemical and physical stabilization capacity of organic C by soil is believed to be mainly governed by clay content, regression analysis showed a positive correlation between SOCS and sand (R = 0.86(**)), whereas a negative correlation with clay (R = -0.77(**)) was observed, thus suggesting that most of this organic C occurs as particulate OM instead of mineral-associated OM. Although the proposed models do not take into account possible changes due to natural and anthropogenic processes, they represent a simple way that could be used to evaluate and/or monitor the potential of each forest plantation in immobilizing organic C in soil (thus reducing atmospheric C concentration), as well as to select more appropriate species during forestation plan management at least in the north of Iran.     

Geochemical characterization and biomonitoring of reclaimed soils in the Po River Delta (Northern Italy): implications for the agricultural activities

This geochemical study is focused on the easternmost part of the Po River alluvial plain in Northern Italy, which is interested by widespread agricultural activities, investigating a reclaimed sector of the Province of Ferrara, known as “Valle del Mezzano” (Mezzano Low Land, hereafter reported as MLL) characterized by peat-rich soils. The chemical–mineralogical characterization of these reclaimed soils is important to compare the local geochemical backgrounds with those recorded in other sectors of the River Po plain and to monitor if the observed concentration exceeds critical thresholds. The reported analyses include (a) measurement of the soil salinity, (b) nutrient evaluation, (c) major and trace element concentrations carried out on bulk soils, (d) tests of metal extraction with both aqua regia and EDTA to highlight the distinct elemental mobility and (e) phyto-toxicological measurement of heavy metal concentrations in plants (Lactuca sativa acephala) grown on the studied soils. The results indicate (1) high soil salinity, often with drastic increase of sodium and chloride along the soil profiles, (2) high nitrogen content (in part related to anthropogenic activities) on superficial horizons and nitrate decrease along the soil profiles and (3) comparative enrichments in heavy metals with respect to other soils of the province, which indicate that peat deposits are effective in trapping metals from anthropogenic sources. This, in turn, implies potential geochemical risks for the agricultural activities. In this regard, specific concerns are related to the high nickel and arsenic content of MLL soils due to the mobility of these elements and their attitude to be taken up by plants.     

Effects of climate change on surface-water photochemistry: a review

Information concerning the link between surface-water photochemistry and climate is presently very scarce as only a few studies have been dedicated to the subject. On the basis of the limited knowledge that is currently available, the present inferences can be made as follows: (1) Warming can cause enhanced leaching of ionic solutes from the catchments to surface waters, including cations and more biologically labile anions such as sulphate. Preferential sulphate biodegradation followed by removal as organic sulphides in sediment could increase alkalinity, favouring the generation of the carbonate radical, CO₃ ^·?. However, this phenomenon would be easily offset by fluctuations of the dissolved organic carbon (DOC), which is strongly anticorrelated with CO₃ ^·?. Therefore, obtaining insight into DOC evolution is a key issue in understanding the link between photochemistry and climate. (2) Climate change could exacerbate water scarcity in the dry season in some regions. Fluctuations in the water column could deeply alter photochemistry that is usually favoured in shallower waters. However, the way water is lost would strongly affect the prevailing photoinduced processes. Water outflow without important changes in solute concentration would mostly favour reactions induced by the hydroxyl and carbonate radicals (·OH and CO₃ ^·?). In contrast, evaporative concentration would enhance reactions mediated by singlet oxygen (¹O₂) and by the triplet states of chromophoric dissolved organic matter (³CDOM*). (3) In a warmer climate, the summer stratification period of lakes would last longer, thereby enhancing photochemical reactions in the epilimnion but at the same time keeping the hypolimnion water in the dark for longer periods.     

Effects of repeated-low level sodium chlorate administration on ruminal and fecal coliforms in sheep

Abstract

The objective of this study was to evaluate the efficacy of oral sodium chlorate administration on reducing total coliform populations in ewes. A 30% sodium chlorate product or a sodium chloride placebo was administered to twelve lactating Dorper X Blackbelly or Pelibuey crossbred ewes averaging 65 kg body weight. The ewes were adapted to diet and management. Ewes were randomly assigned (4/treatment) to one of three treatments which were administered twice daily by oral gavage for five consecutive days: a control (TC) consisting of 3 g sodium chloride/animal/d, a T3 treatment consisting of 1.8 g of sodium chlorate/animal/d, and a T9 treatment consisting of 5.4 g sodium chlorate/animal/d; the latter was intended to approximate a lowest known effective dose. Ruminal samples collected by stomach tube and freshly voided fecal samples were collected daily beginning 3 days before treatment initiation and for 6 days thereafter. Contents were cultured quantitatively to enumerate total coliforms. There were no significant differences in total coliform numbers (log₁₀ cfu/g) in the feces between treatments (P = 0.832). There were differences (P < 0.02) in ruminal coliform counts (log₁₀ cfu/mL) between treatments (4.1, 4.3 and 5.0 log₁₀/mL contents in TC, T3 and T9 Treatments, respectively) which tended to increase from the beginning of treatment until the 5th day of treatment (P < 0.05). Overall, we did not obtain the expected results with oral administration of sodium chloride at the applied doses. By comparing the trends in coliform populations in the rumen contents in all treatments, there was an increase over the days. The opposite trend occurred in the feces, due mainly to differences among rumen contents and feces in ewes administered the T9 treatment (P = 0.06). These results suggest that the low chlorate doses used here were suboptimal for the control of coliforms in the gastrointestinal tract of ewes.